U.S. patent number 3,956,145 [Application Number 05/440,116] was granted by the patent office on 1976-05-11 for fluid for injection into a subterranean reservoir to displace hydrocarbons in the reservoir.
This patent grant is currently assigned to Texaco Inc.. Invention is credited to Charles A. Christopher, Jr., Abdus Satter.
United States Patent |
3,956,145 |
Christopher, Jr. , et
al. |
May 11, 1976 |
Fluid for injection into a subterranean reservoir to displace
hydrocarbons in the reservoir
Abstract
In a subterranean reservoir containing both petroleum and water
interspersed, the petroleum may be preferentially produced by
injecting into one well penetrating the reservoir a slug of fluid
comprising hydrocarbon solvent, colloidal silica, water and a
polymeric material followed by a driving fluid comprising water to
force the reservoir fluids into another well penetrating the
reservoir where they are produced.
Inventors: |
Christopher, Jr.; Charles A.
(Houston, TX), Satter; Abdus (Conroe, TX) |
Assignee: |
Texaco Inc. (New York,
NY)
|
Family
ID: |
26981820 |
Appl.
No.: |
05/440,116 |
Filed: |
February 6, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
319067 |
Dec 27, 1972 |
3818989 |
|
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Current U.S.
Class: |
507/212; 166/275;
507/213; 507/937; 507/261; 507/221; 507/225; 507/229; 507/230;
507/224; 516/34; 516/22 |
Current CPC
Class: |
C09K
8/82 (20130101); C09K 8/905 (20130101); E21B
43/20 (20130101); Y10S 507/937 (20130101) |
Current International
Class: |
E21B
43/16 (20060101); E21B 43/20 (20060101); C09K
8/82 (20060101); C09K 8/90 (20060101); C09K
8/60 (20060101); E21B 043/22 () |
Field of
Search: |
;166/273,274,275,282,283
;252/8.55D,309,310,313S,8.55R ;260/42.55,29.6MH |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Guynn; Herbert B.
Attorney, Agent or Firm: Whaley; T. H. Ries; C. G. Priem;
Kenneth R.
Parent Case Text
This is a division, of application Ser. No. 319,067, filed Dec. 27,
1972, now Pat. No. 3,818,989.
Claims
We claim:
1. A fluid for injection into a subterranean hydrocarbon reservoir
to displace hydrocarbons in the reservoir which comprises a mixture
of hydrocarbon solvent in an amount sufficient to provide
miscibility with hydrocarbons contacted in the reservoir, an amount
of colloidal silica having a particle size ranging from about 7 to
15 millimicrons and a surface area of from about 50 to about 400
meters .sup.2 /gram sufficient to thicken the solvent, water in an
amount sufficient to emulsify the hydrocarbon solvent and a high
molecular weight polymer selected from the group consisting of
polyarylamides, polysaccharides produced by the bacterium
Xanthomonas campestris, water soluble starch derivatives containing
carboxyl, sulfonate or sulfate group, polyvinyl alcohol, polyvinyl
pyrrolidone, poly (arylic acid), poly (ethylene oxide) and
polyethyleneimines in an amount sufficient to migrate from the
mixture into the water present in the reservoir and reduce
permeability of the reservoir to water.
2. A fluid as in claim 1 wherein the fluid also contains 0.5 weight
percent or less of surfactant.
3. A fluid as in claim 1 wherein the fluid also contains less than
0.5 weight percent of a multifunctional compound selected from the
group consisting of ethylene glycol and propylene glycol.
4. A fluid as in claim 1 wherein the fluid also contains less than
0.5 weight percent of a surfactant and a multifunctional compound
selected from the group consisting of ethylene glycol and propylene
glycol.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention pertains to the field of secondary and tertiary
recovery of oil.
2. Description of the Prior Art
Petroleum in subterranean reservoirs, hereinafter referred to as
oil, is often driven to production wells by encroaching water. This
encroaching water may come, for example, from a large expanding
aquifer. On the other hand water may have been injected into the
reservoir to drive oil toward a production well as part of a
secondary recovery operation. In either case a large amount of oil
is likely to be left behind in the portion of the reservoir
encountered by water. The recovery of this oil is complicated by
many factors. One factor is the retentive forces tending to keep
the oil from moving toward a production well. These factors are
viscosity and capillarity. The other factor complicating the
production of this oil is the fact that normal production methods
in the reservoir where water encroachment has taken place will tend
to produce large amounts of water along with the oil. This water
presents a problem of disposal in handling which greatly affects
the economics of an oil recovery program.
The oil left behind after water encroachment is often produced by
injecting a fluid into the reservoir to drive or displace the oil
in the reservoir to a production well. This procedure is called
secondary recovery in the case where the encroaching water which
swept through the reservoir in the first instance was due to
natural forces. i.e., aquifer expansion. Where the injection of a
fluid to produce oil follows another artificially induced attempt
to add energy to the reservoir (water injection, gas injection, in
situ combustion, etc.) the injection of fluid is called tertiary
recovery. For simplicity, hereinafter all attempts to inject a
fluid into a reservoir to displace oil toward a production well
will be referred to as secondary recovery techniques regardless of
the sequence or number of events prior to the instant recovery
program.
In addition to oil production, the water in the reservoir will also
be produced in large quantities as discussed above. Also, as
mentioned above, the forces of viscosity and capillarity tend to
reduce oil production. The retentive forces of viscosity may be
removed, for example, by heating the formation to a point where the
viscosity of the reservoir fluid becomes equal to or less than the
viscosity of the displacing fluid or by increasing the viscosity of
the displacing fluid. However, if the displacing fluid is not
miscible with the oil the retentive forces of capillarity will not
be removed. To remove the retentive forces of capillarity, for
example, it is necessary to use a displacing fluid which is
miscible with the oil. If the displacing fluid is miscible with the
reservoir oil the interface between the oil and displacing fluid
will be removed and, therefore, so will the retentive forces of
capillarity.
Displacement efficiency is a term referring to amount of oil
removed from the portion of the reservoir actually swept by the
displacing fluid. Displacement efficiency may be low due to high
surface tension at the interface between the displacing fluid and
the oil in the reservoir. If this surface tension can be removed
the capillary forces will be reduced to zero and the oil may be
completely displaced from the portions of the reservoir contacted
by the displacement fluid.
Sweep efficiency is a term referring to the percentage of the
reservoir actually contacted or swept by the displacing fluid
regardless of the amount of oil removed from the swept portion or
displacement efficiency referred to above. A major cause of poor
sweep efficiency is associated with the fact that the injected
displacement fluid generally has a lower viscosity than the oil to
be displaced.
If the viscosity of the fluid displacing the reservoir oil to the
production wells is lower than the reservoir oil, premature
breakthrough of the driving fluid into the production wells will
occur. The displacing fluid actually fingers through the reservoir
and proceeds to the production well before an adequate portion of
the reservoir has been swept. The effects of viscosity on sweep
efficiency may be described in terms of the mobility ratio. The
mobility ratio is defined by the following equation: ##EQU1## where
M = mobility ratio;
u.sub.2, u.sub.1 = viscosity of displacing fluid and displaced
fluid (oil), respectively;
K.sub.2, K.sub.1 = permeability of the formation with respect to
the displacing fluid and the displaced fluid respectively.
At high mobility ratios the phenomenon commonly known as
"fingering" occurs and the displacing fluid does not display a flat
front to the reservoir oil but instead rushes ahead at various
points in finger-like protrusions which may prematurely break
through to the production wells. The oil in areas not touched by
the fingers of displacing fluid are usually left unrecovered in
pockets in the reservoir. These pockets are isolated and are likely
to be lost forever. The preceding equation shows that the mobility
ratio and the degree of fingering is directly proportional to the
ratio of the displaced fluid viscosity to the displacing fluid
viscosity u.sub.1 /u.sub.2. Since most displacing fluids are less
viscous than the displaced fluid (oil) the mobility ratio will
usually be quite high and a poor aerial sweep efficiency will occur
because of fingering.
This invention provides a method for increasing the amount of oil
production relative to water production by solving the problems of
viscosity and capillarity inhibiting oil production or providing at
the same time a method of retarding water production.
SUMMARY OF THE INVENTION
The invention is a method for recovering oil from subterranean
reservoirs containing both oil and an aqueous fluid. The reservoir
is penetrated by at least one injection well and one production
well. A displacing fluid is injected into the injection well and
oil is produced from the production well. The fluid comprises a
slug of a mixture of hydrocarbon solvent, colloidal silica, water
and a high molecular weight polymer followed by another fluid to
drive the slug through the reservoir. The invention is also the
novel displacing fluid.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a typical situation in an oil bearing reservoir as
the driving fluid of the invention travels from an injection well
to a production well.
FIG. 2 is a plot showing the advantages of using the method of our
invention in an oil reservoir containing a high water
saturation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
It often happens that a subterranean oil reservoir will contain a
large amount of water or aqueous fluid such as brine in addition to
the oil. This water or aqueous fluid may have originated from the
natural soruces such as an aquifer or it may have been introduced
by artificial means.
In a reservoir containing large amounts of water as well as oil the
mobility of water (K.sub.w /u.sub.w, water effective
permeability/water viscosity) is very large compared with the
mobility of oil (K.sub.o /u.sub. o, oil effective permeability/oil
viscosity). Our invention will reduce the mobility of water
relative to oil by increasing the viscosity of an oil-miscible slug
and/or decreasing the formation permeability to water and/or
increasing the viscosity of injected and formation water. Our
invention will also increase the oil displacement efficiency by
injecting into the reservoir a fluid, a portion of which is
miscible with oil but substantially immiscible with water. These
things will be accomplished using a novel fluid to displace the
reservoir fluids.
The novel displacing fluid comprises a solvent for the petroleum,
thickened with colloidal silica or some other suitable material to
increase the viscosity of the solvent to the range of the reservoir
oil and emulsified with a water or brine solution of a high
molecular weight polymer. Preferably, a surfactant or
multi-functional material is added to improve the stability of the
emulsion and to reduce the surface tension holding the oil to
mineral surfaces. A slug of this primary displacing fluid is
followed by continuous injection of another fluid, such as water or
brine.
By way of explanation of the effects of such a displacing slug on
the reservoir fluid the following is offered. However, the
operation of our invention is not meant to be limited to specific
mechanisms and the following is offered only to enable those
skilled in the art to better understand our invention.
1. The oil-miscible thickened solvent portion of the slug forms a
stable front against the oil since the mobility of the thickened
solvent approaches that of the displaced reservoir oil. Also, since
the solvent is miscible with oil the retentive force of capillarity
impeding oil movement is removed. Therefore, fingering is reduced
and increased displacement and aerial sweep efficiency is
achieved.
2. The emulsion of water and polymer comes in contact with the
water in the reservoir and some polymer is lost to the reservoir
water. This lost polymer increases the viscosity of the reservoir
water and permanently reduces the permeability of the reservoir to
this water. This decreases the mobility of the reservoir water.
3. After injection of the slug comprising petroleum solvent,
colloidal silica, water and polymer, another less expensive
material, water or brine, for example, is injected to push the slug
through the formation. The front of this following water is
continuously thickened with polymer from the slug. Thus, the
mobility of the trailing water and the slug will approach each
other and the aerial sweep efficiency and displacement efficiency
of the trailing water will be enhanced. Alternatively, the leading
edge of the trailing water may be thickened before injection with a
suitable material.
The size of the slug may vary over wide limits dictated by
reservoir conditions and economics. The size of the slug is not
critical to our invention as long as enough driving fluid is
present to efficiently sweep the reservoir. For example, a slug of
about 5 to 50% of pore volume should be satisfactory. For most
applications a slug of from about 15 to 25% or pore volume is
preferred.
The hydrocarbon solvent component of the slug of our invention must
be a solvent for the reservoir hydrocarbons, that is, it must be
miscible with the reservoir hydrocarbons. Examples of typical,
suitable hydrocarbons are aromatics such as benzene and toluene and
aliphatics such as LPG, propane, butane, isobutane, pentane,
isopentane and hexane. Also, any mixture of suitable hydrocarbon
solvents which when mixed retain their miscibility characteristics
with the reservoir hydrocarbons are acceptable. An especially
useful solvent would be a light cut from lease crude. Other
solvents will occur to those skilled in the art without departing
from the scope of our invention.
Colloidal silica is preferred as a thickener for the solvent
portion of the slug in our invention. The colloidal silica
acceptable for use in the method of this invention should have a
particle size ranging from about 7 to 15 millimicrons (mu). In this
size range the colloidal silica will pass through even reservoirs
with very small pore sizes. For example, a reservoir having very
low permeability of say 0.16 millidarcies (md) has a
correspondingly small pore size of 25 to 100 microns. Thus, the
colloidal silica suitable for use in the process of this invention
will pass through even the smallest pores encountered in
subterranean hydrocarbon reservoirs and will maintain a constant
viscosity in the displacing fluid.
The colloidal silica useful in our invention is different from
precipitated silica or silica gel. The colloidal silica useful in
our invention is a fused silica which is made up of chain-like
formations sintered together. These chains are branched and have
enormous external surface areas of from about 50 to about 400
meters.sup.2 /gram. Each segment in the chain has many hydroxyl
(OH) groups attached to silicon atoms at the surface. When the
segments come into proximity to each other these hydroxy groups
will bond to each other by hydrogen bonding to form a
three-dimensional network. Colloidal silicas are readily available
commercially. One source is the Cabot Corporation of Boston, Mass.
under the trade name CAB-O-SIL. Colloidal silica is also available
from other commercial sources and the reference to one source is
not intended to limit the scope of our invention.
When the silica particles are dispersed in a liquid medium, the
network structure formed by the silica particles restricts the
movement of the molecules of the liquid medium. This in turn
results in an increase in the viscosity of the liquid.
It is known that the thickening efficiency of the silica is
directly related to the polarity of the liquid to be thickened. The
use of selected additives (surfactants and/or multi-functional
compounds) can increase the thickening efficiency of the silica. In
the case of the hydrocarbon solvents, these additives react with
the interface between the silica and the solvent and increase the
degree to which the silica particles form the three-dimensional
network. This allows less silica to be used to achieve equivalent
thickening of the solvents. Usually less than 0.5% of the additive
based on the weight of total liquid to be thickened will achieve
marked increases in viscosity. The use of these optional additives
may not be necessary to the successful operation of our invention.
However, they may be used to optimize the efficiency of the
thickening process.
The surfactant which may be used in the slug of our invention may
broadly be any compound which reduces surface tension of the water,
thus reducing the surface tension between the water and the
reservoir oil. Soap may be used for instance, the sodium salts of
high molecular weight alkyl sulfates or sulfonates. Also, very
useful are nonionic surfactants which are usually a reaction
product of a hydrophobic and a hydrophylic material such as the
reaction product between mixed monoalkyl phenols and ethylene
oxide. For example, low polarity liquids such as most hydrocarbon
solvents are normally thickened by the use of anionic surfactants
such as sodium linear alkyl sulfonates and multi-functional
compounds such as a glycol. Ethylene glycol, propylene glycol are
typical examples of useful multi-functional compounds which may be
used. Other equivalents will be apparent to one skilled in the
art.
The water portion of the slug of this invention may be fresh water
or water containing various degrees of inorganic salts such as
brine.
The polymer portion of the slug of our invention may be any polymer
which will reduce the effective permeability to water of the
formation behind the displacing fluid slug. The polymer will
migrate from the slug into the water present in the reservoir to
accomplish the permeability reduction. Typical examples of suitable
polymers include polyacrylamides having from about 0 to about 75%
of the amide groups hydrolyzed to carboxylate groups. It is
preferred to have from about 0 to 30% of the amide group hydrolyzed
to carboxylate groups. Especially preferred is a polyacrylamide of
greater than 6 million molecular weight and approximately 5% of the
amide groups hydrolyzed. Polysaccharides are also polymers useful
in our invention. For example, a commercially available material is
Kelzan MF (a xanthan gum produced by the action of the bacterium
Xanthomonas campestris). Modifications of polysaccharides to
increase their ionic character will make them even more useful in
our invention.
Another type of polymer useful in our invention are water soluble
starch derivatives containing carboxyl sulfonate or sulfate groups
in the form of sodium or ammonium salts. Other useful polymers
include but are not limited to soluble cellulose derivatives,
polyvinyl alcohol, polyvinyl pyrrolidone, poly (arylic acid), poly
(ethylene oxide) and polyethyleneimines. This listing is not
exhaustive. Various other polymers may be used without departing
from the scope and spirit of our invention. The following is a
typical method of preparing the novel driving fluid or slug of our
invention. It is given for illustration only and is not intended to
limit the scope of our invention in any way. Other methods of
preparation will no doubt become apparent to one skilled in the art
after learning from the teachings found herein.
FORMING THE NOVEL DRIVING FLUID
To a volume of water is added 20% by weight colloidal silica with
rapid stirring. A polar additive is added in an amount from 5 to 20
percent of the amount of colloidal silica added. Stirring forms a
gel. The hydrocarbon solvent is added in an amount about equal to
the original water volume with stirring. A solution of polymer in
water is now added. The concentration of the polymer in the water
will typically range from about 250 milligrams/liter (mg/l) to
about 2000 mg/t. A preferred concentration is about 750 mg/t.
The displacing fluid described above may now be diluted with water
and/or solvent to obtain a typical fluid having a viscosity of
about 10 centipoise (cp). The fluid has the approximate
composition: 100 mg/l polymer, 800 mg/l colloidal silica, 400 mg/l
surfactant, 80% solvent and 20% water. The compositions possible
are infinite and may be formulated using the above teachings by one
skilled in the art.
One of the most critical criteria for formulating a driving fluid
is the viscosity needed. The optimum viscosity of a driving slug is
that which causes a mobility ratio of about one between the slug
and the reservoir oil. The slug may be adjusted in viscosity by the
general techniques previously described.
FIG. 1 depicts a cut-away view of an oil reservoir 12 which has
previously been waterflooded and contains an oil saturation S.sub.o
of 30% and a water saturation S.sub.w of 70%. The reservoir is
penetrated by an injection well 10 and a production well 11, both
wells being in fluid communication with the reservoir. The driving
slug 14, comprising colloidal silica, water, solvent and polymer,
was injected into the injection well 10 and has traveled some
distance out into the reservoir. The area 13 is that portion of the
reservoir as yet untouched by the driving slug 14. The area 15
behind the driving slug contains very little oil (S.sub.o about 2%)
and contains polymer absorbed from the slug onto the reservoir rock
or mechanically entrapped. Relative permeability to water has been
reduced by a factor of at least 3. The slug will continue to push
the oil ahead of it and leave behind most of the water until
breakthrough of the slug occurs at production well 11.
FIG. 2 depicts the results of a mathematical simulation of the
method of our invention performed in a linear reservoir. The
reservoir was modeled having properties as follows:
Thickness, 29 feet
Porosity (fraction), 0.19
Absolute Permeability, 0.194 Darcy
Initial Water Saturation, 65%
Initial Oil Saturation, 35%
Oil Viscosity, 30 centipoise
Distance from Injector to Producer, 330 feet
These fluids were separately injected by simulation. A comparison
was made of the performance of each fluid. The fluid of the
invention, as described earlier, had 100 mg/l polymer, 800 mg/l
colloidal silica, 400 mg/l surfactant, 80% solvent and 20% water.
The other fluid was of like composition except that it contained no
polymer. FIG. 2 shows the results of the performance of these two
fluids. The fluid of the invention containing polymer recovered
34.2% of the oil in place; while the fluid without the polymer
recovered only 22% of the oil in place. Moreover, the fluid of the
invention recovered the oil at a lower water-oil ratio than the
fluid without the polymer. The extremely efficient fluid of the
invention lowered the residual oil saturation to 0.8%.
* * * * *